US2393737A - Preparation of unsaturated esters - Google Patents

Preparation of unsaturated esters Download PDF

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US2393737A
US2393737A US578937A US57893745A US2393737A US 2393737 A US2393737 A US 2393737A US 578937 A US578937 A US 578937A US 57893745 A US57893745 A US 57893745A US 2393737 A US2393737 A US 2393737A
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esters
ester
preparation
hydrocarbon group
alkali metal
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Newman M Bortnick
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Rohm and Haas Co
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Rohm and Haas Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
    • C07C67/327—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups by elimination of functional groups containing oxygen only in singly bound form

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  • This invention relates to a process for prep'aring acrylic and alkacrylic esters. More particularly, this invention deals with the preparation of such esters by thermally decomposing esters of p-alkoxypropionic acid and a-hydrocarbon substituted fl-alkoxypropionic acids in the presence or an alkali metal alcoholate.
  • esters of p-alkoxypropionic acid and p-alkoxy-a-hydrocarbon substituted propionic acids are converted to acrylic and ill-hydrocarbon substituted acrylic esters in good yield when heated at a temperature from about 40 C. to about 190 0., preferably 40 C. to 150 0., with a small amount of an alkali'metal alcoholate as a catalyst.
  • a polymerization inhibitor may be present in the reaction mixture to prevent formation of polymers.
  • Hydroquinone and copper powder are typical inhibitors for this purpose.
  • an alkali metal alcoholate lithium, sodium, and potassium alcoholates having been found eifective.
  • The; alcoholate may desirably be used in amountsfrom 0.01 to 0.10 mol per mol of alkoxy ester.
  • the alcoholate selected is preferably, but not necessarily, the same as that occurring in the ester, a pure, unmixed product then resulting, since there is no chance of ester interchange. Alcoholates which do not correspond with th alcohol residue or residues in the alkoxy esters are, however, operable .and satisfactory for the preparation of the unsaturated esters.
  • R is a primary aliphatic hydrocarbon group
  • R is an aliphatic hydrocarbon group
  • X is hydrogen or a lower alkyl group, including methyl, ethyl, propyl, or butyl.
  • the compounds in which X is hydrogen or methyl are of primary importance at the present time. The same byat normal pressures.
  • drocarbon group may occur for both R and R or different groups may be used, in which case the unsaturated product is apt to consist of a mixture of esters as the result of alcoholysis.
  • Typical groups for R include methyl, ethyl, propyl, butyl, hexyl, octyl, allyl, or methallyl, while R may be any of these groups and also decyl, dodecyl, cetyl, octadecyl, oleyl, or other aliphatic hydrocarbon group.
  • R the hydrocarbon group of an alcohol, such as methyl, ethyl, propyl, allyl, butyl, or amyl, which boils below about 150 C.'so that it may be volatilized readily from the reaction mixture below this temperature
  • Hydrocarbon groups from longer chain alcohols may, however, be used and the alcohols formed therewith volatilized under reduced pressure.
  • the reaction may be carried out by heating the ester of an alkoxypropionic acid with an alkali metal alcoholate and, if desired, distilling the product, preferably with fractionation.
  • the alcohol formed by splitting of the ether group is removed as formed so that the reaction is carried to completion.
  • free alcohol may be used as a solvent and distilled off as the reaction proceeds.
  • the lower alcohols which are those generally used, form constant boiling mixtures with the more volatile unsaturated'esters. Thus, they may be removed from the reaction mixture as rapidly as formed at th lowest feasible temperature.
  • Example 1 was run grams of methyl B-inethoxyisobutyrate, CH3OCH2CH(CH3)COOCH3. About three grams of dry sodium methoxide was added thereto. The flask and contents were heated and all of the liquid distilled from the flask. Temperatures of distillation rose from 63 C. to C. in the vapor and 90 C. to C, in the pot. By analysis, it was found that 50% of the distillate was methyl methacrylate. A gram of sodium methoxide was added thereto and the liquid redistilled. The product was treated with 40% calcium chloride brine to remove the methanol formed in the reaction. The remaining organic liquid was dried withpotassium carbonate and distilled. A yield of 80% of methyl methacrylate was thus obtained.
  • Example 2 A solution of sodium methoxide (0.05 mol) and hydroquinon (0.005 mol) in methanol (10 cc.) was placed in a 'iiask fitted with a fractionating column and a dropping funnel. This solution was heated and methyl p-methoxyisobutyrate (1.0 mol) was added gradually while the cleavage products were distilled oil. Cleavage was very rapid at 90C. The yield of methyl methacrylate was 85% of the theory.,
  • Example 3 A solution of 0.25 gram of sodium was inade in cc. of absolute ethanol. To this solution was added 50 grams of ethyl fi-ethoxypropionate. The mixture was heated below 100 C. and the liquids distilled. The product of this single distillation contained ethyl acrylate corresponding to 70% of the original ethyl ,B-e'thoxypropionate.
  • Example 4 Sodium methoxide (3 grams) was placed in a fiask fitted with a fractionating column containing copper packing and a dropping funnel. Copper turnings were placed in the flask to act as the polymerization inhibitor. Methyl B-methoxyisobutyrate (0.50 mol) dissolved in methanol (1'72 grams) was added gradually, and a 10%-15% solution of methyl methacrylate was obtained in the distillate. No appreciable polymerization took place. 92.5%.
  • esters such as the propyl, butyl, octyl, dodecyl, or higher esters of methoxypropionate, ethoxypropionate, methoxyisobutyrate, ethoxyisobutyrate, or other alkoxy propionic acid or substituted propionic acid having an aliphatic hydrocarbon group in the alpha position.
  • esters such as the propyl, butyl, octyl, dodecyl, or higher esters of methoxypropionate, ethoxypropionate, methoxyisobutyrate, ethoxyisobutyrate, or other alkoxy propionic acid or substituted propionic acid having an aliphatic hydrocarbon group in the alpha position.
  • a process for preparing esters of acrylic and a-alkacrylic acids which comprises heating at a temperature between 40 C. and about 190 C. in the liquid phase in the presence of an alkali metal alcoholate an ester of the formula nocm'cnooon' wherein R is a primary aliphatic hydrocarbon group, R .is an aliphatic hydrocarbon group, and X is a member of the class consisting of hydrogen and lower alkyl groups.
  • esters of acrylic and m-alkacrylic acids which comprises heating at temperatures of 40 C. to about 190 C. in the liquid phase in the presence of an alkali metal alcoholate an ester of the formula nocrm mooon"
  • the yield of methyl methacrylate was wherein R. is a primary aliphatic hydrocarbon group of one to eight carbon atoms, R'is ,a'primary aliphatic hydrocarbon group of one to eighteen carbon atoms, and X is a member of the class consisting of hydrogen and lower alkyl groups.
  • a process for preparing es -e. of acrylic acid which comprises heating at temperatures of 40 C. to about C. in the liquid phase in the presenceof an alkali metal alcoholate an ester of the formula ROCHzCHzCOOR wherein R is a primary aliphatic hydrocarbon group of one to eight carbon atoms and R is a primary alkyl group of one to four carbon atoms.
  • R is a primary aliphatic hydrocarbon group of one to eight carbon atoms and R is a primary alkyl group of one to four carbon atoms.
  • a process for preparing esters. of methacrylic acid which comprises heating at tempera tures above 40 C. and below 190 C. in the liquid phase in the presence of an alkali metal alcoholate an ester of the formula cmoomcncooa' Ha wherein R is a primary alkyl group of one to four carbon atoms.
  • a process for preparing methyl methacrylate which comprises heating at temperatures above 40 C. and below 190 C. in the liquid phase in thepresence of an alkali metal alcoholate an ester of the formula omocmcncoocm HI 8.
  • a process for preparing esters of acrylic acid which comprises heating at temperatures of 40- C. to about 190 C. in the liquid phase in the presence of an alkali metal alcoholate an ester of the formula CHaOCHzCHzCOOR CHsOCHzCHzCOOCHs NEWMAN M. BORTNICK.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Description

Patented Jan. 29, 1946 PREPARATION OF UNSATURATED ESTERS Newman r5. Bortnick, Philadelphia, Pa., assignor to Rohm & Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Application February 20, 1945, Serial No. 578,937
9 Claims. (01266-486) This invention relates to a process for prep'aring acrylic and alkacrylic esters. More particularly, this invention deals with the preparation of such esters by thermally decomposing esters of p-alkoxypropionic acid and a-hydrocarbon substituted fl-alkoxypropionic acids in the presence or an alkali metal alcoholate.
It has heretofore been proposed to prepare acrylic acid and esters of acrylic acid from alkoxypropionic acid and its esters by treatment thereof with strong acids. While such methods have been operative, they present serious dimculties in plant practice. They form, for example, highly corrosive mixtures. They yield acrylic acid even when the initial material is a pure cster. They fall to give as favorable yields as is commercially desirable.
It has now been found that esters of p-alkoxypropionic acid and p-alkoxy-a-hydrocarbon substituted propionic acids are converted to acrylic and ill-hydrocarbon substituted acrylic esters in good yield when heated at a temperature from about 40 C. to about 190 0., preferably 40 C. to 150 0., with a small amount of an alkali'metal alcoholate as a catalyst.
A polymerization inhibitor may be present in the reaction mixture to prevent formation of polymers. Hydroquinone and copper powder are typical inhibitors for this purpose. I
As an alkaline catalyst in this reaction, there is used an alkali metal alcoholate, lithium, sodium, and potassium alcoholates having been found eifective. The; alcoholate may desirably be used in amountsfrom 0.01 to 0.10 mol per mol of alkoxy ester. The alcoholate selected is preferably, but not necessarily, the same as that occurring in the ester, a pure, unmixed product then resulting, since there is no chance of ester interchange. Alcoholates which do not correspond with th alcohol residue or residues in the alkoxy esters are, however, operable .and satisfactory for the preparation of the unsaturated esters.
As alkoxy esters there may be used esters of the formula:
wherein R is a primary aliphatic hydrocarbon group, R is an aliphatic hydrocarbon group, and X is hydrogen or a lower alkyl group, including methyl, ethyl, propyl, or butyl. The compounds in which X is hydrogen or methyl are of primary importance at the present time. The same byat normal pressures.
drocarbon group may occur for both R and R or different groups may be used, in which case the unsaturated product is apt to consist of a mixture of esters as the result of alcoholysis. Typical groups for R include methyl, ethyl, propyl, butyl, hexyl, octyl, allyl, or methallyl, while R may be any of these groups and also decyl, dodecyl, cetyl, octadecyl, oleyl, or other aliphatic hydrocarbon group. It is preferable to have R the hydrocarbon group of an alcohol, such as methyl, ethyl, propyl, allyl, butyl, or amyl, which boils below about 150 C.'so that it may be volatilized readily from the reaction mixture below this temperature Hydrocarbon groups from longer chain alcohols may, however, be used and the alcohols formed therewith volatilized under reduced pressure.
The reaction may be carried out by heating the ester of an alkoxypropionic acid with an alkali metal alcoholate and, if desired, distilling the product, preferably with fractionation. In the most convenient procedure, the alcohol formed by splitting of the ether group is removed as formed so that the reaction is carried to completion. Optionally, free alcohol may be used as a solvent and distilled off as the reaction proceeds. The lower alcohols, which are those generally used, form constant boiling mixtures with the more volatile unsaturated'esters. Thus, they may be removed from the reaction mixture as rapidly as formed at th lowest feasible temperature.
Details of the preparation of typical unsatu rated esters are shown in the following examples.
Example 1 was run grams of methyl B-inethoxyisobutyrate, CH3OCH2CH(CH3)COOCH3. About three grams of dry sodium methoxide was added thereto. The flask and contents were heated and all of the liquid distilled from the flask. Temperatures of distillation rose from 63 C. to C. in the vapor and 90 C. to C, in the pot. By analysis, it was found that 50% of the distillate was methyl methacrylate. A gram of sodium methoxide was added thereto and the liquid redistilled. The product was treated with 40% calcium chloride brine to remove the methanol formed in the reaction. The remaining organic liquid was dried withpotassium carbonate and distilled. A yield of 80% of methyl methacrylate was thus obtained.
Example 2 A solution of sodium methoxide (0.05 mol) and hydroquinon (0.005 mol) in methanol (10 cc.) was placed in a 'iiask fitted with a fractionating column and a dropping funnel. This solution was heated and methyl p-methoxyisobutyrate (1.0 mol) was added gradually while the cleavage products were distilled oil. Cleavage was very rapid at 90C. The yield of methyl methacrylate was 85% of the theory.,
Example 3 A solution of 0.25 gram of sodium was inade in cc. of absolute ethanol. To this solution was added 50 grams of ethyl fi-ethoxypropionate. The mixture was heated below 100 C. and the liquids distilled. The product of this single distillation contained ethyl acrylate corresponding to 70% of the original ethyl ,B-e'thoxypropionate.
Example 4 Sodium methoxide (3 grams) was placed in a fiask fitted with a fractionating column containing copper packing and a dropping funnel. Copper turnings were placed in the flask to act as the polymerization inhibitor. Methyl B-methoxyisobutyrate (0.50 mol) dissolved in methanol (1'72 grams) was added gradually, and a 10%-15% solution of methyl methacrylate was obtained in the distillate. No appreciable polymerization took place. 92.5%.
In place of the methyl and ethyl-esters used above, there may be used esters, such as the propyl, butyl, octyl, dodecyl, or higher esters of methoxypropionate, ethoxypropionate, methoxyisobutyrate, ethoxyisobutyrate, or other alkoxy propionic acid or substituted propionic acid having an aliphatic hydrocarbon group in the alpha position. The lower alkoxypropionates, wherein R is an alkyl group of one to four carbon atoms, yield acrylates and methacrylates of great use in the plastic arts.
I claim:
1. A process for preparing esters of acrylic and a-alkacrylic acids which comprises heating at a temperature between 40 C. and about 190 C. in the liquid phase in the presence of an alkali metal alcoholate an ester of the formula nocm'cnooon' wherein R is a primary aliphatic hydrocarbon group, R .is an aliphatic hydrocarbon group, and X is a member of the class consisting of hydrogen and lower alkyl groups.
2. A process for preparing esters of acrylic and m-alkacrylic acids which comprises heating at temperatures of 40 C. to about 190 C. in the liquid phase in the presence of an alkali metal alcoholate an ester of the formula nocrm mooon" The yield of methyl methacrylate was wherein R. is a primary aliphatic hydrocarbon group of one to eight carbon atoms, R'is ,a'primary aliphatic hydrocarbon group of one to eighteen carbon atoms, and X is a member of the class consisting of hydrogen and lower alkyl groups.
3. A process for preparing es -e. of acrylic acid which comprises heating at temperatures of 40 C. to about C. in the liquid phase in the presenceof an alkali metal alcoholate an ester of the formula ROCHzCHzCOOR wherein R is a primary aliphatic hydrocarbon group of one to eight carbon atoms and R is a primary alkyl group of one to four carbon atoms. 4. A process for preparing esters of a-alkacrylic acids which comprises heating at temperatures of 40 .C. in the liquid phase in the presence of an alkali metal alcoholate an ester of the formula ROCHzCHCOOR wherein R is a primary aliphatic hydrocarbon group of one to eight carbon atoms and R is a primary alkyl group of one to four carbon atoms.
6. A process for preparing esters. of methacrylic acid which comprises heating at tempera tures above 40 C. and below 190 C. in the liquid phase in the presence of an alkali metal alcoholate an ester of the formula cmoomcncooa' Ha wherein R is a primary alkyl group of one to four carbon atoms.
7. A process for preparing methyl methacrylate which comprises heating at temperatures above 40 C. and below 190 C. in the liquid phase in thepresence of an alkali metal alcoholate an ester of the formula omocmcncoocm HI 8. A process for preparing esters of acrylic acid which comprises heating at temperatures of 40- C. to about 190 C. in the liquid phase in the presence of an alkali metal alcoholate an ester of the formula CHaOCHzCHzCOOR CHsOCHzCHzCOOCHs NEWMAN M. BORTNICK.
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2457225A (en) * 1946-05-01 1948-12-28 Du Pont Preparation of acrylates
US2531512A (en) * 1946-11-05 1950-11-28 Union Carbide & Carbon Corp Process for making sorbic acid esters
US2921090A (en) * 1955-03-08 1960-01-12 Celanese Corp Production of sorbic acid
DE1124482B (en) * 1958-06-25 1962-03-01 Wacker Chemie Gmbh Process for the preparation of acrylic acid esters and ª ‡ -alkylacrylic acid esters by splitting off alcohol from ª ‰ -alkoxymonocarboxylic acid esters
DE1124481B (en) * 1958-06-03 1962-03-01 Wacker Chemie Gmbh Process for the preparation of acrylic acid and ª ‡ -alkyl acrylic acid esters by splitting off alcohol from ª ‡ or ª ‰ -alkoxymonocarboxylic acid esters
DE1124483B (en) * 1958-06-03 1962-03-01 Wacker Chemie Gmbh Process for the preparation of acrylic acid and ª ‡ -alkyl acrylic acid esters by splitting off alcohol from ª ‡ - or ª ‰ -alkoxymonocarboxylic acid esters
DE1125912B (en) * 1958-06-03 1962-03-22 Wacker Chemie Gmbh Process for the preparation of acrylic acid esters and ª ‡ -alkylacrylic acid esters by splitting off alcohol from ª ‰ -alkoxymonocarboxylic acid esters
US3267133A (en) * 1962-03-12 1966-08-16 Eastman Kodak Co Process for preparing 2, 2-dimethylalkyl acrylates and methacrylates
DE1279015B (en) * 1961-12-29 1968-10-03 Wacker Chemie Gmbh Process for the preparation of acrylic acid esters by splitting ª‰-alkoxycarboxylic acid esters
US3666805A (en) * 1965-03-12 1972-05-30 Lonza Ag Preparation of methacrylic acid
EP1357105A1 (en) * 2002-04-25 2003-10-29 Nippon Shokubai Co., Ltd. Decomposition of a Michael type adduct of acrylic acid or acrylic acid ester

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2457225A (en) * 1946-05-01 1948-12-28 Du Pont Preparation of acrylates
US2531512A (en) * 1946-11-05 1950-11-28 Union Carbide & Carbon Corp Process for making sorbic acid esters
US2921090A (en) * 1955-03-08 1960-01-12 Celanese Corp Production of sorbic acid
DE1124481B (en) * 1958-06-03 1962-03-01 Wacker Chemie Gmbh Process for the preparation of acrylic acid and ª ‡ -alkyl acrylic acid esters by splitting off alcohol from ª ‡ or ª ‰ -alkoxymonocarboxylic acid esters
DE1124483B (en) * 1958-06-03 1962-03-01 Wacker Chemie Gmbh Process for the preparation of acrylic acid and ª ‡ -alkyl acrylic acid esters by splitting off alcohol from ª ‡ - or ª ‰ -alkoxymonocarboxylic acid esters
DE1125912B (en) * 1958-06-03 1962-03-22 Wacker Chemie Gmbh Process for the preparation of acrylic acid esters and ª ‡ -alkylacrylic acid esters by splitting off alcohol from ª ‰ -alkoxymonocarboxylic acid esters
DE1124482B (en) * 1958-06-25 1962-03-01 Wacker Chemie Gmbh Process for the preparation of acrylic acid esters and ª ‡ -alkylacrylic acid esters by splitting off alcohol from ª ‰ -alkoxymonocarboxylic acid esters
DE1279015B (en) * 1961-12-29 1968-10-03 Wacker Chemie Gmbh Process for the preparation of acrylic acid esters by splitting ª‰-alkoxycarboxylic acid esters
US3267133A (en) * 1962-03-12 1966-08-16 Eastman Kodak Co Process for preparing 2, 2-dimethylalkyl acrylates and methacrylates
US3666805A (en) * 1965-03-12 1972-05-30 Lonza Ag Preparation of methacrylic acid
EP1357105A1 (en) * 2002-04-25 2003-10-29 Nippon Shokubai Co., Ltd. Decomposition of a Michael type adduct of acrylic acid or acrylic acid ester
US6870066B2 (en) 2002-04-25 2005-03-22 Nippon Shokubai Co., Ltd Method for decomposition of Michael type adduct

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